US20020041822A1 - Aluminum filler alloy containing sodium for fluxless brazing - Google Patents

Aluminum filler alloy containing sodium for fluxless brazing Download PDF

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Publication number
US20020041822A1
US20020041822A1 US09/885,529 US88552901A US2002041822A1 US 20020041822 A1 US20020041822 A1 US 20020041822A1 US 88552901 A US88552901 A US 88552901A US 2002041822 A1 US2002041822 A1 US 2002041822A1
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Prior art keywords
alloy
brazing
aluminum
filler
controlled atmosphere
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Abandoned
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US09/885,529
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English (en)
Inventor
David Childree
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Kaiser Aluminum and Chemical Corp
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Kaiser Aluminum and Chemical Corp
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Priority to US09/885,529 priority Critical patent/US20020041822A1/en
Assigned to KAISER ALUMINUM & CHEMICAL CORPORATION reassignment KAISER ALUMINUM & CHEMICAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHILDREE, DAVID L.
Publication of US20020041822A1 publication Critical patent/US20020041822A1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
    • B23K35/286—Al as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/08—Non-ferrous metals or alloys
    • B23K2103/10—Aluminium or alloys thereof

Definitions

  • the present invention relates, in general, to an aluminum filler metal that contains silicon (Si) and intentional additions of sodium (Na) or Na+bismuth (Bi) or Na+potassium (K), or Na+Bi+K.
  • Si silicon
  • Na Na+bismuth
  • K Na+potassium
  • the combination of a core alloy and the new filler metals is brazed in a furnace with an inert, non-oxidizing atmosphere without the need of a flux.
  • Fluxless brazing is not a new or revolutionary concept when brazing aluminum materials.
  • Vacuum brazing was the main joining process for aluminum for about 20 years.
  • the principles behind vacuum brazing were relatively simple, i.e., Mg was needed in the filler alloy to sublime and breach the tenacious oxide film on the brazing sheet surface.
  • the pressure level was reduced to about 5 ⁇ 10 ⁇ 5 Torr while simultaneously heating the furnace to the brazing temperature near 1112° F. (600° C.).
  • the pressure-temperature combination allowed Mg in the filler metal to sublime and disrupt the Al 2 O 3 film on the surface of the sheet.
  • Mg also reacts with the Al 2 O 3 film to form MgAl 2 O 4 , a Mg-spinel.
  • the Mg-spinel is more friable than Al 2 O 3 and more easily disrupted when the Mg sublimed.
  • Magnesium spinels are also more easily wetted by molten aluminum. This combination of reaction, sublimation disruption, and wetting characteristics allowed vacuum brazing to become a commercial success.
  • Typical core alloys had post-braze strength levels around 10 ksi (69 MPa).
  • Vacuum brazing was, however, not without its problems.
  • Major problems included capital equipment costs that were high, fit-up tolerances that were carefully controlled, surface cleanliness had to be very good, vacuum furnace atmosphere had to be carefully controlled, and furnace maintenance was hazardous due to Mg-rich deposits that could ignite when cleaning.
  • NOCOLOKTM brazed assemblies could be dirtier, fit-up tolerances were less critical, capital equipment costs were significantly less, and the leak rate of brazed cores was near zero.
  • NOCOLOKTM brazing process has some limitations.
  • the NOCOLOKTM process was developed by Alcan in 1976, but it was not commercially adopted until about 1988.
  • the NOCOLOKTM brazing describes a process in which a potassium cryolite (KAlF 4 -K 3 AlF 6 ) powder is suspended in a water carrier and sprayed onto a heat exchanger surface. After spraying the potassium cryolite slurry onto the component, the water is evaporated in a drying oven before brazing. Next, the component to be brazed is placed into a control atmosphere brazing (CAB) furnace with a nitrogen atmosphere and brazed. During the heating cycle, the flux melts about 10° F. (5° C.) to 15° F.
  • CAB control atmosphere brazing
  • the flux melts, it dissolves the oxide on the aluminum sheet surfaces to create a nascent surface that the filler metal can now wet.
  • the component is cooled to about 500° F. (260° C.) or lower before it exits the furnace.
  • Flux poisoning refers to a reaction that occurs between the KAlF 4 -K 3 AlF 6 and Mg.
  • the resulting product is MgF 2 , a very stable compound that prevents the NOCOLOKTM flux from dissolving the flux.
  • increasing the flux loading to counter increasing core alloy Mg levels appears to be an effortless way to solve the problem at hand.
  • most of the commercial heat exchanger producers have found that increasing the flux loading in excess of 5 g/m 2 results in significantly higher production costs.
  • brazing sheet materials were typically comprised of Mg-free 4XXX filler alloys clad to 3003 (Mg-free) core alloys. From Table 1 it is clear that raising the Mg level is desirable to increase the post-braze strength of the core alloy. Increasing the core alloy strength translates to thinner wall structures, lighter assemblies, and a potential costs savings since less material would be needed to make a heat exchanger.
  • the present invention is a product and process for fluxless brazing of aluminum materials in an inert, non-oxidizing atmosphere.
  • the product is an aluminum filler metal that contains silicon and sodium.
  • bismuth and/or potassium may be added with the sodium.
  • the present brazing process includes brazing under controlled atomospheric conditions. Preferably, the brazing occurs in an inert atmosphere containing high levels of nitrogen or argon.
  • the intentional addition of sodium or sodium in combination with potassium and/or bismuth results in a fluxless brazing with core alloys having a greater amount of magnesium.
  • the increased levels of magnesium in the core alloy yield an increased post-brazing strength of the core alloy.
  • the present invention is a truly fluxless aluminum brazing process that does not require a vacuum furnace, NOCOLOKTM (fluoride flux) flux or other costly, unique capital equipment.
  • NOCOLOKTM fluoride flux
  • the filler material can be clad to core alloys preferably from the 3XXX, 5XXX, or 6XXX alloys described by the Aluminum Association, for example, a 3005-type alloy preferably containing about 0.5% magnesium.
  • Increasing the amount of magnesium in the core alloy results in an increased post-braze strength of the core alloy.
  • the quality of the atmosphere in the furnace is important to obtaining the above identified advantages.
  • Acceptable joints are formed when the inert gas contains preferably less than about 100 ppm of oxygen. Such preferred inert atmospheres include nitrogen or argon gases.
  • the present invention comprises a filler alloy and a brazing process in a controlled, inert environment using the filler alloy, where the filler is comprised of about 4 to 20 wt % silicon and intentional additions of sodium, or sodium and bismuth, or sodium and potassium, or sodium, bismuth and potassium. More preferably, the levels of sodium range from about 0.0008 to 0.06 wt. %, potassium levels range from about 0.0005 to 0.03 wt. %, and bismuth levels range from about 0.03 to 0.133 wt. %.
  • the balance of the material contains aluminum and incidental impurities, for example, iron, copper, and magnesium up to about 1 wt. % and manganese up to about 1.5 wt. %.
  • FIGS. 1 A- 1 C are sketches of a mini-radiator test sample used to evaluate the influence of the subject invention clad metal alloy compositions on the tube-to-header fillet size;
  • FIGS. 2 A- 2 C are sketches of a “box-ring” sample used to evaluate the effect of sample geometry on the fillet size of the clad alloys constructed in accordance with the preferred embodiments of the present invention
  • FIG. 3 is a graph of the average fillet areas of the fluxless brazing process of the present invention in a nitrogen atmosphere using a K366 (0.5% Mg) core with 4045 filler alloys containing sodium or sodium and bismuth, with the materials being cleaned by wiping with acetone;
  • FIG. 4 is a graph of the average fillet areas of the fluxless brazing process of the present invention in a nitrogen atmosphere using a K366 (0.5% Mg) core with 4045 filler alloys containing sodium or sodium and bismuth, with the materials being cleaned with a Trenton aqueous cleaner;
  • FIG. 5 is a graph of the average fillet areas of the fluxless brazing process of the present invention in a nitrogen atmosphere using a K366 (0.5% Mg) core with 4045 filler alloys containing sodium or sodium and bismuth, with the being cleaned by vapor degreasing in 1-1-1 trichloromethane; and
  • FIG. 6 is a graph showing the comparison of the brazing filler alloys of the present invention with a number of control alloys.
  • the present invention relates generally to the brazing of aluminum articles in which sodium is intentionally added to an aluminum filler to facilitate fluxless brazing.
  • the addition of sodium alone or in combination with potassium and/or bismuth to the filler material allows increased levels of magnesium to be introduced into the core alloy resulting in a core alloy of higher strength.
  • the brazing is performed in a controlled environment having an inert atmosphere.
  • the controlled environment contains high levels of nitrogen or argon.
  • CAB controlled atmosphere brazing
  • Core means an aluminum alloy which is the structural support for the aluminum alloy that is used as the filler.
  • Filler means an aluminum alloy which is used to braze the core or other aluminum articles.
  • Core is used to describe the use of the filler when it is overlaid on one or both surfaces of the core. Thereafter, the clad core is called a composite or a brazing sheet. “Fillet” means a concave junction between two surfaces.
  • the presently preferred filler alloy contains aluminum as a major constituent, and also contains silicon and sodium. Sodium is intentionally added to achieve the desired beneficial properties, and may also be added to the alloy in combination with bismuth and/or potassium. The addition of bismuth and/or potassium tightens the performance variation or improves overall performance of the alloy.
  • the preferred alloy has the above elements in the following ranges as measured by weight percent (wt. %).
  • the amount of silicon in the filler alloy is from about 4% to 20%.
  • the preferred level of sodium is from about 0.0008% to 0.06%, with a more preferred range from about 0.005% to 0.05%, and a most preferred range from about 0.006% to 0.03%.
  • the preferred level of bismuth is from about 0.03% to 0.133%, with a more preferred range from about 0.03% to 0.1%, and a most preferred range from about 0.03% to 0.08%.
  • the preferred level of potassium, again if added to the alloy is from 0.0005% to 0.03%, having a more preferred range from about 0.001% to 0.03%.
  • the balance of the filler alloy contains aluminum and incidental impurities.
  • the incidental impurities may comprise iron, copper, magnesium and manganese.
  • the weight percentages for iron, copper and magnesium are typically below 1%, and usually are below 0.3%. In the case of magnesium, the level must be kept below about 0.1%.
  • the amount of manganese can be up to about 1.5% without adversely affecting the brazeability of the alloy.
  • the filler alloy is generally employed in the form of a brazing sheet rolled from ingots having the desired alloy composition.
  • the filler is applied to the surface of the aluminum core alloy through cladding regardless of the brazing process. Cladding of the aluminum core alloy with the filler is accomplished by methods well-known in the art, for example by pressure welding through a rolling process. Preferably, the material is partially annealed in dry nitrogen. After rolling and partial annealing, the sheets are cleaned and assembled into desired parts, for example, mini-radiators samples of the type illustrated in FIGS. 1 A-C.
  • FIG. 1A shows a top view of the pre-braze sample and
  • FIG. 1B shows a side view of the pre-braze sample.
  • FIG. 1C shows the post-braze sample.
  • the parts are then brazed in a furnace containing an inert gas, preferably nitrogen or argon.
  • the preferred incoming gas has about 100 ppm of oxygen or less.
  • the filler alloys were clad, i.e. roll bonded, to a K366 core alloy.
  • This alloy is a 3005-type alloy containing about 0.5% Mg and processed to develop long life corrosion performance.
  • This core alloy was selected to show that the new filler metals could be fluxless brazed while clad to a high strength core alloy.
  • the compositional range for the K366 core alloy is described in Table 3. TABLE 3 Compositional range of the K366 and K383 core alloys. Ele- ment Si Fe Cu Mn Mg Cr Ti Each Others K366 0.10 0.25 0.28- 1.00- 0.39- 0.05 0.05 0.05 0.15 max. max. 0.38 1.30 0.51 max. max. max. max. max. K383 0.10 0.3 0.20- 1.00- 0.05 0.05 0.05 0.05 0.15 max. max. 0.40 1.30 max. max. max. max. max. max.
  • All core-clad composites (hereafter, referred to as materials) were rolled into sheets that are 0.013 inches (0.330 mm) thick.
  • the clad layer i.e., filler metal
  • All materials were partial annealed to the H24 temper in dry nitrogen.
  • the sheet samples were cleaned in different commercial cleaners and assembled into the mini-radiator samples depicted in FIG. 1.
  • the mini-radiators approximate commercially produced radiator or heater core joints. All samples were brazed in a furnace with a nitrogen cover gas.
  • the preferred incoming gas had about 100 ppm of O 2 or less.
  • a commercially made brazing sheet material was used as the control material.
  • the control material was a long life material with a core alloy designated K383 and filler alloy of AA4343. A detailed description of the core and filler alloy compositions is shown in Tables 2 and 3.
  • the control material was 0.0125′′ (0.3175 mm) thick with the liner comprising 10% of the total sheet thickness. Normally, the control material would be coated with 3 to 5 g/m 2 of NOCOLOK flux, then brazed in a furnace with an inert atmosphere. However, the control material was compared to the new materials without the benefit of flux. The control material was given the same preparation and cleaning as the new materials.
  • FIGS. 2 A-C show the box ring samples made with the brazing sheet.
  • FIG. 2A shows the top view
  • FIG. 2B shows the end view
  • FIG. 2C shows the side view.
  • the box ring samples permit evaluation of two joint geometries with one test specimen. In this test, the quality of the two joint geometries is visually rated and compared to a standard.
  • a test specimen made with the sodium containing aluminum alloy filler material material no. 025 was acetone cleaned and brazed without flux.
  • Several test specimens were made and brazed in furnace atmospheres consisting of increasing oxygen levels in the nitrogen, as shown in Table 4. TABLE 4 Calibrated nitrogen gas oxygen levels. Run No. Oxygen Level, ppm Nitrogen Level, % 1 50 Balance 2 60 Balance 3 70 Balance 4 80 Balance 5 150 Balance
  • Control material coated with 1 g/m 2 of flux was also tested, assembled into a box ring test specimen, and brazed in the atmospheres described in Table 4.
  • the chamber is evacuated to remove the lab atmosphere.
  • the furnace atmosphere can be purged with nitrogen before beginning the brazing thermal cycle. If the furnace is evacuated, the cycle takes two minutes. Purging requires that the equivalent of three to four furnace chamber volume exchanges occur before beginning the braze cycle.
  • test specimens typically required 22 minutes to reach 590° C. (1095° F.).
  • test specimen reached 590° C. (1095° F.), heating was terminated.
  • test specimen temperature will coast up to 599° C. (1110° F.) in approximately 5 minutes.
  • test specimen will continue to gain heat until it reaches approximately 604° C. (1120° F.), at which time the gas begins to cool the test specimen.
  • the total soak time in the temperature range or 599° C. (1110° F.) to 604° C. (1120° F.) is about 4 minutes.
  • test specimen has cooled to 571° C. (1060° F.) or lower, it is removed and air cooled.
  • test specimens were evaluated by microsectioning, mounting, and polishing through the centerline of the tube sections.
  • the fillet areas of the tube-to-header samples were examined on an optical metallograph and measured with quantitative image analysis software.
  • Test specimens made from the control material were also given identical cleaning treatments and brazed without flux. This was done to determine if any of the cleaners had an unexpected effect on the brazeability of the new materials. If an effect was observed, it would not be possible to positively determine whether the new alloys are a success. Fillet areas of the new materials were compared to conventionally NOCOLOKTM fluxed and brazed test specimens. Two large data bases, developed in 1993 and 1998, containing information generated using the mini-radiator test specimen served as a baseline to judge the performance of the new materials. In order for the new materials to be considered a success, the brazing performance of the new materials must be similar to the incumbent NOCOLOKTM flux brazing process.
  • Example 1 the sample materials were cleaned by wiping their surfaces with acetone only.
  • the purpose of the acetone wipe was to establish baseline brazing performance of the sample materials.
  • Acetone as a cleaner was selected since it easily removes most common oils and greases from aluminum sheet surfaces without chemically reacting or interacting with the aluminum substrate.
  • the mini-radiator specimens were placed into a furnace normally used for control atmosphere brazing (CAB) of specimens coated with NOCOLOKTM flux. The test specimens were brazed by using the furnace thermal cycle described earlier. None of the acetone cleaned test specimens were NOCOLOKTM fluxed. As we can see in FIG. 3, the sample materials developed fillet areas that were equivalent to the control materials treated with NOCOLOKTM flux. However, the control material that was not fluxed and acetone wiped did not form any fillets.
  • Trenton cleaner is a commercial caustic cleaner which contains NaOH. Sample materials were cleaned in the Trenton cleaner and were fluxless brazed as was done in Examples 1. The data plotted in FIG. 4 indicates that the Trenton cleaner had a beneficial effect on the sample materials. However, the control material cleaned in the Trenton cleaner did not produce any fillets. Cleaning the sample materials in the Trenton cleaner produced fillet areas that were about the same size as the control materials that were NOCOLOKTM fluxed and brazed.
  • the Trenton cleaner in combination with the sodium containing aluminum fluxless brazing materials developed the largest fillets.
  • a larger number of the material compositions described in Table 2 were examined. All materials were cleaned in the Trenton cleaner and fluxless brazed.
  • the data plotted in FIG. 6 shows the fillet areas developed in the mini-radiator test specimens after fluxless brazing. It was found that all the new materials do not develop acceptable fillet sizes relative to the NOCOLOKTM fluxed control materials. However, there were some materials that developed acceptable fillet sizes relative to the control material treated with NOCOLOKTM flux.
  • FIG. 6 The data shown in FIG. 6 clearly shows that increasing the Bi to fairly high levels results in increasingly small fillets.
  • FIG. 6 also shows that the combination of Na and K result in the largest mini-radiator fillet areas.
  • the effect of high levels of K and Bi combined with Na results in small fillet areas.
  • the data plotted in FIG. 6 indicates that each element must be maintained in a critical range, individually or in combination, to develop fillet sizes rival NOCOLOKTM fluxed and brazed materials.
  • Table 5 ranks the sensitivity of the Na-containing materials to the quality of the atmosphere. TABLE 5 Effect of increasing oxygen levels in nitrogen on the brazeability of the new Na-containing materials Oxygen Na-Only Control with Run Level, Nitrogen Rating 1 g/m 2 flux No. ppm Level * Rating* 1 50 Balance 5 5 2 60 Balance 4 5 3 70 Balance 3 5 4 80 Balance 3 3 5 150 Balance 1 2

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US09/885,529 2000-06-22 2001-06-21 Aluminum filler alloy containing sodium for fluxless brazing Abandoned US20020041822A1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007512143A (ja) * 2003-11-28 2007-05-17 アルカン レナリュ アルミニウム合金製の帯材のロウ付け方法
US8413876B2 (en) * 2003-11-28 2013-04-09 Constellium France Aluminium alloy strip for brazing
JP2016203193A (ja) * 2015-04-17 2016-12-08 株式会社Uacj アルミニウム合金シート及びその製造方法、ならびに、当該アルミニウム合金シートを用いたアルミニウムブレージングシート

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108467975B (zh) * 2018-06-20 2019-12-17 辽宁忠旺集团有限公司 一种3系铝合金管材的生产工艺

Family Cites Families (3)

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Publication number Priority date Publication date Assignee Title
US4173302A (en) * 1969-12-15 1979-11-06 Vereinigte Aluminium-Werke Aktiengesellschaft Process and alloy for brazing aluminum-containing articles
SU436715A1 (ru) * 1973-02-19 1974-07-25 Всесоюзный Научно-Исследовательский Институт По Нормализации В Машиностроении Припой дл бесфлюсовой пайки алюмини и его сплавов
US5728479A (en) * 1995-11-03 1998-03-17 Childree; David L. Aluminum-lithium-magnesium filler alloy for brazing

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007512143A (ja) * 2003-11-28 2007-05-17 アルカン レナリュ アルミニウム合金製の帯材のロウ付け方法
US20070158386A1 (en) * 2003-11-28 2007-07-12 Alcan Rhenalu Aluminium alloy strip for brazing
US7926701B2 (en) * 2003-11-28 2011-04-19 Alcan Rhenalu Method for brazing strips of aluminium alloy
US8413876B2 (en) * 2003-11-28 2013-04-09 Constellium France Aluminium alloy strip for brazing
JP2016203193A (ja) * 2015-04-17 2016-12-08 株式会社Uacj アルミニウム合金シート及びその製造方法、ならびに、当該アルミニウム合金シートを用いたアルミニウムブレージングシート

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CA2413246A1 (fr) 2001-12-27
WO2001098019A1 (fr) 2001-12-27
AU2001272022A1 (en) 2002-01-02

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